Meta-anilide ureas as algicidal agents

ABSTRACT

This invention relates to the utility of certain meta-anilide ureas of the general formula   WHEREIN R is selected from the group consisting of alkyl, haloalkyl, 2,4-dichlorophenoxy-methylene, monochlorophenyl, dichlorophenyl and the sodium salt of pentafluoroethyl; R&#39;&#39; is selected from the group consisting of hydrogen, lower alkyl and lower alkoxy; and R&#39;&#39;&#39;&#39; is lower alkyl as algicidal agents.

United States Patent [191 Baker et al.

[451 May 27, 1975 META-ANILIDE UREAS AS ALGICIDAL AGENTS [75] Inventors: Don R. Baker, Orinda; Eugene G.

Teach, El Cerrito, both of Calif.; Duane R. Arnekley, Antelope, Mont.

[73] Assignee: Stautfer Chemical Company,

Westport, Conn.

[22] Filed: Apr. 9, 1973 [21] Appl. No.: 349,529

OTHER PUBLICATIONS Fitzgerald Wisconsin Academy of Sciences, Arts and 1 Letters, Vol. 46, (1957), pgs. 281-294.

Primary Examiner-Lewis Gotts Assistant ExaminerCatherine L. Mills Attorney, Agent, or Firm-Harry A. Pacini; Daniel C. Block; Edwin H. Baker [5 7] ABSTRACT This invention relates to the utility of certain metaanilide ureas of the general formula II NHC-R ll II wherein R is selected from the group consisting of alkyl, haloalkyl, 2,4-dichlorophenoxy-methylene, monochlorophenyl, dichlorophenyl and the sodium salt of pentafluoroethyl; R is selected from the group consisting of hydrogen, lower alkyl and lower alkoxy; and R" is lower alkyl as algicidal agents.

37 Claims, N0 Drawings META-ANILIDE UREAS AS ALGICIDAL AGENTS l1 IiTHC-R RI .NHCN\RH wherein R is selected from the group consisting of alkyl having 1 to 8 carbon atoms, inclusive, haloalkyl having 1 to 4 carbon atoms, inclusive, 2,4- dichlorophenoxymethylene, monochlorophenyl and the sodium salt of pentafluoroethyl; R is selected from the group consisting of hydrogen, lower alkyl having 1 to 4 carbon atoms, inclusive, R" is lower alkyl having 1 to 4 carbon atoms, inclusive. It was found that these compounds have an algicidal effect and provide beneficial results in controlling the growth of algae.

Controlling the growth of algae by employing the compounds described herein can be accomplished by applying an algicidally effective amount to the environment in which algae growth is encouraged. The compounds maybe applied toanyenvironmental area K which is a host to algae or susceptible to algae attack and growth. By controlling, it is meant the inhibition and prevention of the growth of the organism to be controlled. I i g The termu lower alkyl and flower alkoxy, as used herein, i.e., both in the specification and claims, contemplates linear and branched chain alkyl radicals containing from 1 to 4 carbon-atoms, inclusive, such as methyl, methoxy, ethyl, ethoxy, n-propyl, n-propoxy, isopropyl, isopropoxy, njbutyl, n-butoxy, iso-butyl, isobutoxy,"sec.-butyl, secz-butoxy, tert.-butyl and tert.-

butoxy.

The term alkyl perferably includes linear and branched chain alkyl radicals containing from 1 to 8 I carbon' atoins, inclusive, such as methyl, ethyl, n-

methyl, mo n o chlor .oet1iyl, dichloroethyl, trichloroethyl, pentachloroethyl, bromomethyl, bromoethyl, trifluoro methyl, pentafiuoroethyl, chlorofluoromethyl, chlorofluoroethyl, ..monofluorotetrachloroethyl, lbromol -methylethyl, l ,1 -dimethyl-2-chloroethyl and the like.

The following compounds in Table I can be used, for

example, accordingito theinvention hereindescribed.

Compound numbers haveabeemassigned and are used throughout the balance of this application.

TABLE I Commp. C.

pound Number R R R" or NJ 1 C- ,F CH CH 150.5-157 2 (C1 H CH 142-448 3 2,4-diCl-phenyl CH CH 102-107 4 C- F -Nu Salt CH CH 99-105 5 C F; OCH CH;, 118-119 6 CF;, CH CH 178-184 7 CH O-2.4-diCl- CH CH 146-148 phenyl 8 C(CH C H; H CH 146448 9 C(CH;,) C;,H H C H 1.5258 10 CH C(CH;,);, H C.,H,-, 166-169 1 l CH CH(CH;;) H n-C H,. 1 13-1 l6 l2 CH C(CH;,); H n-QH, 73-78 13 CH CH(CH=;)C H,-, H CH 139-142 14 CBr(C1-l;,) H CH 121 15 CH C(CH C H H CH 163-166 16 CH(C H )C ,H H CH 162-164 17 CCI CH CH CH 155-159 18 CC1 CF H CH 151-154 19 CCI CF CH CH l 1O 2O C F H C 11 l94l96 21 (3 1 CH nC.,H 105-108 22 C(CH CH Cl CH nC ,H,, glass 23 CH(C H,-,) CH nC H,, glass 24 CH(CH )C H CH n-C H,, glass 25 CH-;C(CH3):; CH nC H., glass 26 CCL, OCH;, CH 148-150 27 CF;, OCH;, CH 28 C l-1 OCH CH 107-1 10 29 t-C H,, OCH CH 1.5463 30 CH(CH;;)C;;H OCH CH 1.5463 31 C(CH H OCH CH 1.5410 32 3-Cl-phenyl OCH CH,, 1.5943 33 2,4-diCl-pheny1 OCH CH;, 1.5 823 34 2,4-diCl-phenyl- OCH CH 139-143 OCH:

The compounds mentioned thus far, and those contemplated, can be producted, for example, according to the following methods.

The compounds of the present invention are prepared by several methods. Two such methods applicable in preparing the compounds are the condensation between the appropriate metaamino substituted anilide with either an isocyanate or carbamoyl chloride and also the condensation of the appropriate meta-amino urea and either an acyl halide or acid anhydride. These methods will be further exemplified below. When the unsubstituted amidophenyl urea is prepared a cyanate salt is reacted with the appropriate substituted amido anilide. The reactions proceed readily in the liquid phase. The employment of a solvent is also useful, facilitating processing, as well as agitation of the reactants. Solvents such as water, benzene, toluene, acetone, tetrahydrofuran, and the like, are employed. A catalyst may be employed to enhance the reaction although a catalyst is not required. The reactions are carried out at temperatures that permit operation in the liquid phase. These temperatures are between about room temperature and reflux temperature of the solvent if a solvent is employed. Preferably, the reaction mixture is refluxed at an elevated temperature.

The following illustrated examples describe in detail, without restriction thereto, the preparation of representative compounds. U.S. Pat. No. 3,642,891 teaches the preparation of the compounds of this invention. Reference is hereby made to U.S. Pat. No. 3,642,891, the disclosure of which is hereby incorporated by reference. The foregoing patent specified hereinabove basically discloses preparation techniques for the compounds utilized in the method of the present invention.

EXAMPLEI Preparation of 1(3 pentafluoropropionamidophenylllidimethyl urea.

To 108 g. of meta aminophenyldimethyl urea in 100 ml. of acetone and 6.1 g. of triethylamine was added by bubbling into the solution 110 g. of pentafluoropropionylchloride. The triethylaminehydrochloride salt was filtered and the solvent evaporated. The viscous oil then obtained was dissolved in methylene chloride. A white crystalline product was obtained. This was filtered and dried in a vacuum oven. There was obtained 4.5 g. of the title compound, m.p. l50.5l57C.

in a similar procedure, l(3'- pentafluoropropionamidophenyl)3-methyl-3-methoxy urea was prepared.

EXAMPLE 11 Preparation of l(3-pentafluoropropionamidophenyl) 3.3-dimethyl urea-Sodium Salt.

To a quantity of l(3-pentafluoropropionamidophenyl)3.3-dimethyl urea (16.3 g.) dissolved in 100 ml. of methanol was added 25% solution of sodium methoxide in methanol. The solvent was removed under vacuum. There was obtained 17.9 g. of the title compound, m.p. 99105C.

EXAMPLE Ill Preparation of 3'dimethylureido-2,4-dichlorobenzanilide.

To 9.0 g. of 3'-aminophenyldimethyl urea dissolved in 100 ml. of acetone containing 5.5 g. of triethylamine was added 10.5 g. of 2,4-dichlorobenzoyl chloride. There was obtained 16.2 g. of the title compound, m.p.

l02l07C.

Also prepared in a similar procedure as hereinabove described was the compound, l-(3'- trichloroacetamidophenyll-3-methyl urea.

The following examples are given for the purpose of illustrating the algicidal properties according to the instant invention.

ALGICIDAL TEST PROCEDURE Sufficient candidate toxicant is diluted in acetone to give an 0.5% mixture which is then diluted into 20 milliliters of warm modified Jack Meyers Agar Medium I.Algae Culture from Laboratory to Pilot Plant, 1953, Page 94). The dilutions selected concentrations of from 0.5 ,ug/mL. to 50 ug/ml, including 1.0, 5.0 and 10.0 ,ug/mL, of the test compound in 20 X 100 mm. Petri dishes. After the agar solidifies, separate Petri dishes are innoculated with the desired organism, such as Scenedesmus obliquus or Chlorella pyrenoidosa. The innoculated samples are then allowed to grow at room temperature under fluorescent lamps using a 14 hour light period each day. After 1 to 2 weeks, depending upon the growth of the untreated controls, the results are recorded as to the level necessary to control the specific organism. The results obtained with representative compounds and their concentrations are given in Table l1.

TABLE I1 ALGlClDE TEST COMPOUND (concentration, (concentration, NUMBER #g/ml.) #g/ml.)

8 50 50 9 50 50 1O (50) 50 I 1 50 (50) 12 50 50 13 50 50 14 (50) 50 15 (50) (5) 16 50 (5) 17 50 (5) I8 50 l 19 (50) l 20 50 (1) 21 (50) l 22 50 (50) 23 (50) (50) 24 5O 50 25 50 50 26 (5) l 27 50 (1) 28 50 50 29 (50) (5) 30 (50) l 31 5O 5 32 50 l 33 (50) 5 34 (l) l i denotes not tested l denotes partial control at the indicated concentration.

The manner in which the water area may be treated for the control of algae will vary with the specific problems encountered. An acute problem in the storage and utilization of industrial process water is the fouling of such water and systems in which the water is used by the growth of algae. Entire areas such as a pond or lake may be treated. Drainage ditches and other waterflowing sites may be treated.

In addition to use in ponds and lakes, this invention is applicable to the control of algae in industrial cooling towers and other water recirculating systems as used in paper manufacturing processes, for example.

The substances to be employed according to the present invention can be used as such or in the form of formulations with carrier vehicles. Examples and emulsifiable concentrates, spray powders, pastes, soluble powders, and the like. Suitable carrier vehicles or assistants are mainly: Solvents, such as, optionally chlorinated, aromatic hydrocarbons (e.g., xylene, benzene, chlorobenzenes), paraffms (e.g., petroleum fractions), alcohols (e.g., methanol, ethanol, butanol), amines (e.g., ethanolamine, dimethyl formamide), as well as water; finely divided solid carriers, for example, natural and synthetic stone meals or powders (kaolin, alumina, chalk, i.e., calcium carbonate, talc, highly disperse silicic acid, silicates, e.g., alkali silicates); emulsifiers, such as non-ionic and anionic emulsifiers (e.g., polyoxyethylene fatty acid esters and polyoxyethylene fatty acid esters and polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) especially magnesium stearate, sodium oleate, etc., and dispersing agents such as lignin, sulfite waste liquors and methyl cellulose.

As already mentioned above, the active compounds or agents to be employed according to the instant invention can be present in the aforesaid formulations in mixture with one another and with other known active substances. I

The algicidal compositions of the invention also comprise aqueous emulsions. The aqueous emulsions can be prepared by dissolving a surfactant of the type noted hereinabove and pouring the emulsifiable concentrate so obtained into water with vigorous agitation. The aqueous emulsions of the invention can also be prepared by dissolving the active ingredient in a watermiscible solvent such as Carbitol (diethylene glycol monoethyl ether), acetone, a lower alkanol, Cellosolve (ethylene glycol monoethyl ether), dioxan, and the like, if desired, in association with a surfactant such as noted above, to obtain an emulsifiable concentrate which is poured into water with vigorous agitation. The aqueous emulsions of the invention can also be prepared by dissolving the active ingredient and a surfactant such as noted above in an organic solvent which is immiscible with water. The resulting emulsifiable concentrate is then admixed with water with vigorous agitation to form an emulsion. The water-immiscible organic solvents which are suitable for use include cyclohexanone, summer oils, aromatic hydrocarbons such as benzene, toluene, xylene, and high-boiling petroleum hydrocarbons such as kerosene, diesel oil, and the like.

The aqueous emulsions of the invention can be supplied to the user in the form of the emulsifiable concentrates described above which require dilution with water before use. Both the concentrated compositions and the diluted compositions are included within the scope of the present invention.

Formulations contain, in accordance with the present invention, in general from 0.l to 95, preferably 0.5 to 90, per cent by weight of active compound or agent. The agents according to the present invention or their preparations are applied in the usual way, e.g., by spraying, dusting, sprinkling or atomizing. The active substances can be applied, according to the purpose in view, in a concentration of 5 to 0.00057c. In special cases it is, however, possible or even necessary to go below or above these concentrations. The remainder of active algicidal composition being an adjuvant which can be a liquid extending agent or surface active agent, but preferably is an admixture thereof.

Various changes and modifications are possible without departing from the spirit and scope of the invention described herein and will be apparent to those skilled in the art to which it pertains.

What is claimed is:

l. The method for inhibiting and preventing algae growth in water, which comprises adding to the algae environment an algicidally effective amount of a compound of the formula 3 IIIHC-R RI Q 1 NhEN\R wherein R is selected from the group consisting of alkyl having 1 to 8 carbon atoms, inclusive, haloalkyl having 1 to 4 carbon atoms, inclusive, 2,4-

LII

dichlorophenoxymethylene, monochlorophenyl, dichlorophenyl and the sodium salt of pentafluoroethyl; R is selected from the group consisting of hydrogen, lower alkyl having 1 to 4 carbon atoms, inclusive, and lower alkoxy having 1 to 4 carbon atoms, inclusive, R" is lower alkyl having 1 to 4 carbon atoms, inclusive.

2. The method of claim 1 wherein R is haloalkyl, R is lower alkyl and R is lower alkyl.

3. The method of claim 2 in which R is pentafluoroethyl, R is methyl and R is methyl.

4. The method of claim 2 wherein R is trifluoromethyl, R is methyl and R is methyl.

5. The method of claim 2 in which R is 1,!- dichloroethyl, R is methyl and R is methyl.

6. The method of claim 2 in which R is l.l-dichloro- 2,2,2-trifluoroethyl, R is methyl and R" is methyl.

7. The method of claim 2 in which R is pentafluoroethyl, R is methyl and R is n-butyl.

8. The method of claim 2 in which R is 2-chloro-l,ldimethylethyl, R is methyl and R is n-butyl.

9. The method of claim 1 in which R is haloalkyl, R is hydrogen and R is lower alkyl.

10. The method of claim 9 in which R is trichloromethyl and R is methyl.

11. The method of claim 9 in which R is 1,l-dichloro- 2,2,2-trifluoroethyl and R is methyl.

12. The method of claim 9 in which R is pentafluoroethyl and R is ethyl.

13. The method of claim 1 in which R is dichlorophenyl, R is lower alkyl and R is lower alkyl.

14. The method of claim 13 in which R is 2,4- dichlorophenyl, R is methyl and R" is methyl.

15. The method of claim 1 in which R is haloalkyl, R is lower alkoxy and R is lower alkyl.

16. The method of claim 15 in which R is pentafluoroethyl, R is methoxy and R" is methyl.

17. The method of claim 15 in which R is trichloromethyl, R is methoxy and R is methyl.

18. The method of claim 15 in which R is trifluoromethyl, R is methoxy and R is methyl.

19. The method of claim 1 in which the R is the sodium salt of pentafluoroethyl, R is lower alkyl and R is lower alkyl.

20. The method of claim 19 in which R is methyl and R" is methyl.

21. The method of claim 1 in which R is monochlorophenyl, R is lower alkoxy and R is lower alkyl.

22. The method of claim 1 in which R is dichlorophenyl, R is lower alkoxy and R is lower alkyl.

' 23. The method of claim 1 in which R is 2,4- dichlorophenoxymethylene, R is lower alkoxy and R is lower alkyl.

24. The method of claim 1 in which R is alkyl, R is lower alkoxy and R is lower alkyl.

25. The method of claim 1 in which R is alkyl, R is lower alkyl and R is lower alkyl.

26. The method of claim 25 in which R is lethylpropyl, R is methyl and R is n-butyl.

27. The method of claim 25 in which R is lmethylbutyl, R is methyl and R is n-butyl.

28. The method of claim 25 in which R is 2,2- dimethylpropyl, R is methyl and R is n-butyl.

29. The method of claim 1 in which R is alkyl, R is hydrogen and R is lower alkyl.

30. The method of claim 29 in which R is 1,1- dimethylbutyl and R is methyl.

7 8 I 31. The method of claim 29 in which R is 1,1- 35. The method of claim 29 in which R is 2- dimethylbutyl and R" is ethyl. methylbutyl and R" is methyl.

The method Of Claim in which R 2,2- 3 The method of in which R is 2 dmethylpropyl and R ethyl dimethylbutyl and R" is methyl.

33. Th m th (1 of cla'm 29 i which R is 2- methylprjpyljnjw 5 37. The method of claim 29 in which R is 1- 34. The method of claim 29 in which R is 2,2- y p y and ismethyll dimethylpropyland R is nbutyl. 

1. THE METHOD FOR INHIBITING AND PREVENTING ALGAE GROWTH IN WATER, WHICH COMPRISES ADDING TO THE ALGAE ENVIRONMENT AN ALGICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA
 2. The method of claim 1 wherein R is haloalkyl, R'' is lower alkyl and R'''' is lower alkyl.
 3. The method of claim 2 in which R is pentafluoroethyl, R'' is methyl and R'''' is methyl.
 4. The method of claim 2 wherein R is trifluoromethyl, R'' is methyl and R'''' is methyl.
 5. The method of claim 2 in which R is 1,1-dichloroethyl, R'' is methyl and R'''' is methyl.
 6. The method of claim 2 in which R is 1,1-dichloro- 2,2,2-trifluoroethyl, R'' is methyl and R'''' is methyl.
 7. The method of claim 2 in which R is pentafluoroethyl, R'' is methyl and R'''' is n-butyl.
 8. The method of claim 2 in which R is 2-chloro-1,1-dimethylethyl, R'' is methyl and R'''' is n-butyl.
 9. The method of claim 1 in which R is haloalkyl, R'' is hydrogen and R'''' is lower alkyl.
 10. The method of claim 9 in which R is trichloromethyl and R'''' is methyl.
 11. The method of claim 9 in which R is 1,1-dichloro- 2,2,2-trifluoroethyl and R'''' is methyl.
 12. The method of claim 9 in which R is pentafluoroethyl and R'''' is ethyl.
 13. The method of claim 1 in which R is dichlorophenyl, R'' is lower alkyl and R'''' is lower alkyl.
 14. The method of claim 13 in which R is 2,4-dichlorophenyl, R'' is methyl and R'''' is methyl.
 15. The method of claim 1 in which R is haloalkyl, R'' is lower alkoxy and R'''' is lower alkyl.
 16. The method of claim 15 in which R is pentafluoroethyl, R'' is methoxy and R'''' is methyl.
 17. The method of claim 15 in which R is trichloromethyl, R'' is methoxy and R'''' is methyl.
 18. The method of claim 15 in which R is trifluoromethyl, R'' is methoxy and R'''' is methyl.
 19. The method of claim 1 in which the R is the sodium salt of pentafluoroethyl, R'' is lower alkyl and R'''' is lower alkyl.
 20. The method of claim 19 in which R'' is methyl and R'''' is methyl.
 21. The method of claim 1 in which R is monochlorophenyl, R'' is lower alkoxy and R'''' is lower alkyl.
 22. The method of claim 1 in which R is dichlorophenyl, R'' is lower alkoxy and R'''' is lower alkyl.
 23. The method of claim 1 in which R is 2,4-dichlorophenoxymethylene, R'' is lower alkoxy and R'''' is lower alkyl.
 24. The method of claim 1 in which R is alkyl, R'' is lower alkoxy and R'''' is lower alkyl.
 25. The method of claim 1 in which R is alkyl, R'' is lower alkyl and R'''' is lower alkyl.
 26. The method of claim 25 in which R is 1-ethylpropyl, R'' is methyl and R'''' is n-butyl.
 27. The method of claim 25 in which R is 1-methylbutyl, R'' is methyl and R'''' is n-butyl.
 28. The method of claim 25 in which R is 2,2-dimethylpropyl, R'' is methyl and R'''' is n-butyl.
 29. The method of claim 1 in which R is alkyl, R'' is hydrogen and R'''' is lower alkyl.
 30. The method of claim 29 in which R is 1,1-dimethylbutyl and R'''' is methyl.
 31. The method of claim 29 in which R is 1,1-dimethylbutyl and R'''' is ethyl.
 32. The method of claim 29 in which R is 2,2-dimethylpropyl and R'''' is ethyl.
 33. The method of claim 29 in which R is 2-methylpropyl and R'''' is n-butyl.
 34. The method of claim 29 in which R is 2,2-dimethylpropyl and R'''' is n-butyl.
 35. The method of claim 29 in which R is 2-methylbutyl and R'''' is methyl.
 36. The method of claim 29 in which R is 2,2-dimethylbutyl and R'''' is methyl.
 37. The method of claim 29 in which R is 1-ethylpentyl and R'''' is methyl. 